Catalytic conversion system



Nov. 20, 1945. M. M. MARlslc CATALYTIC CONVERSION SYSTEM Filed June 14. 1944 M x, l Z. l/ 7 J Lul i 0 Ys fw 5 I\\\ Z l \\\\\l t a V ,n 4 M y f 2 nlyiv Patented Nov. 20, 1945 CATALYTIC CONVERSION SYSTEM Milton M. Marisic, Woodbury, N. J.. assignor to Sooony-Vacuum Oil Company, Incorporated, a corporation oi' New York Application June 14, 1944, Serial No.- 540,293

6Claims.

This invention relates to a. method and apparatus for conducting catalyticA conversion of iiuid materials in the presence of porous ilaments of inorganic oxides having adsorptive and catalytic properties. v

The invention is essentially a method and cor- I responding apparatus for effecting contact between fluids and solids of adsorptive porous nature. Many such operations are known and the invention is not primarily concerned with the nature of the reactions conducted or the composition of the uids and solids brought into contact.

Rather, the invention relates principally to the manner of eectins contact. particularly in oper- .ations where the porous adsorptive solid is alternately contacted with two iluids of different nature and mingling of such iluids is undesirable. A typical example oi processes to which the invention is peculiarly well adapted is continuous catalytic cracking of heavy petroleum fractions to give high yields of' gasoline having good anti-knock properties. During the cracking conversion, a carbonaceous deposit is laid down on the catalyst which reduces the eiliciency thereof rapidly until satisfactory cracking is no longer feasible. The catalyst is then contacted with an oxidizing gas at proper temperature to burn oft the "coke and thereby regenerate the cracking activity of the catalyst which is then re.. turned to contact with hydrocarbons for repetition ot the cracking reaction.

According to the present invention, the porous solid is provided inthe form of nlaments oi potous inorganic oxides fabricated into a flexible sheet or bundle as by weaving, knitting, braiding. twisting, etc. The bundle oi iilaments is passed alternately through separated chambers wherein the two contacting operations are performed and purging ot iiuid from the bundle is eiiected upon withdrawal from' each chamber. To accomplish this successive passing through the two chambers, the bundle or sheet of iilamentous inorganic oxides is formed into an endless belt or rope.

ally weak gelatinous precipitates which are often referred to erroneously as gela A very satsfactory process of this type is described in the copending application of Milton M. Marisic and Edward M. Griest. Serial Number 529.822, illed April 6, 1944. According to the process of that application, a gelable sol is formed and aged to the stage where the viscosity has increased to a considerable extent, but the colloid still has the flow characteristics oi a liquid, i. e., a gel of structure has not been formed. The viscous liquid so prepared, which is known as a jelly is injected into ammonia, either gaseous or as an aqueous solution. This causes immediate coagulation to a firm hydrogel.

In forming nyrogel laments by this process, an acid solution was prepared by mixing 2.60 liters of 38% hydrochloric acid (1.19 speciiic gravity) with 4 liters of a solution containing 885 grams of A12(SO4)3-18H2O and making the total Ivoluume of the solution equal to 10.25 liters. A second solution was prepared by diluting 18.7 pounds of N brand sodium silicate (28.7% SiOz. 8.9% Nano) with water to form 17 liters oi solution. These two solutions were mixed by adding the latter solution to the former while agitating the acid-solution eiiciently with a mechanical stirrer; The resultant colloidal solution had a pH of 0.3.

A portion of the hydrosol was neutralized to a pH of 2.5 to form a Jelly by careful addition of aqueous ammonia while eiciently mixing the sol. This jelly was extruded through a spinneret of the type used in spinning rayon but having holes of. considerably larger size, about l/ioo inch, into. a bath of aqueous ammonia. The jelly coagulated immediately to ilaments oi hydrogel which were partially dried to a water content o! 25 to 40% in order to increase their strength for iurther processing. The partially dried iilaments were collected as a loose skein and were washed with water and soaked in a 15% solution o! mmomomoi..

The iilaments oi inorganic oxides are advan-l The filaments were then dried and woven into a tageously preparedby any one ot several methods. Two very satisfactory methods ailordins good control over porosity and composition of the iilaments are extrusion o! colloidal solutions into coagulatingl baths capable oi forming true hydrol gels o! the sols and leaching oi treated silicate Fllamcnts are formed oi true hydrogels by forming colloidal solutions which can be coagulated to drm hydrogels without forming the structurbelt in which form they were heated to1100 F.

and tested as a cracking catalyst by passing Oklahoma City gas oil in contact with the catalyst at 800 F. and a liquid space velocity of 1.5

for twenty minutes. A yield of 52% of 400 F. endpoint gasoline was obtained,

IAlternatively, the hydrosol may be heated at '15 C. lfor two hours or aged at room temperature for 12 hours to lform the Jelly which is extruded into the ammonia bath.

acid to dissolve out the phase poor in silica, leav- 1o ing a porous body consisting principally of silica.

In a typical example, a glass having the composition or '15% S102, 5% NazO and 20% B103 was prepared and the molten glass was spun to provide glass ibers. The fibers were heat treated at 1050 F. overnight, cooled and extracted with 3.5 normal nitric acid until substantially all of the acid soluble phase of the glass was dissolved. Because of the very small diameter of the glass fibers, this extraction takes little time, usually not over five minutes. 'I'he bers were then washed with water until free of soluble matter and then soaked overnight in a 15% solution of A1(NO:)3'8H2O. The salt solution was poured oil. and the fibers were dried at 180 F. and grad- 25 ually heated to 1l00 F. at which temperature they were maintained for four hours. During the heating step, the aluminum nitrate was converted Ito alumina, giving a catalyst containing 87.7% S102, '1.4% Anoa, 4.6% B203 and 0.3% 30 NazO. When tested under the conditions outlined above, this catalyst gave a yield of of 410 F. endpoint gasoline.

Catalytic bers prepared according to the above examples, or in any other suitable manner,

are fabricated into sheets, ropes or the like by conventional means and the fabricated bodies areA formed, either at the time of fabrication or afterward, into endless belts. The belts are then mounted to pass continuously in a cyclic path i0 including two chambers and means are interposed in said path between the chambers for purging from the fabricated catalyst, fluids retained by the catalyst, as by occlusion, adsorption, etc.

Suitable apparatus for such a `process is shown 4,5

in the annexed drawing, wherein:

Figure 1 is a vertical section through a compartmented chamber for practicing the invention;

Figure 2 is a flow sheet illustrating a plant 50 unit for the process; and

Figure 3 is a view similar to that of Figure 1 showing a modified embodiment.

As shown in Figure 1, an endless belt I0 formed of catalyst bers is passed Ithrough chambers II and I2 provided by a partition I3 in a vessel Il. Rollers I5 and I6 in the upper portions of the chambers and rollers I1 and I8 below the partition carry the catalyst belt and provide positive drive therefor. tition dips into a pool I0 of a liquid which is inert to the catalyst and the gases in the two chambers and which is a stable liquid at the conditions of temperature and pressure prevailing in the vessel II. A molten metal, lead for example, is very o5 well suited for the purpose.

Within each of the loops formed by the upper and lower runs of .the catalyst belt is an inlet 20, 2l to admit gaseous reactant to the chambers for contact with the catalyst. Outlets 22 and '23 79 are provided to withdraw from chamber I I, gaseous products of contact with catalyst belt I0 and outlets 2| and 25 serve a similar purpose in chamber I2.

The lower end of the parating conditions. It is self adjusting for variations in differences in pressure between the two chambers Il and I2, the liquid level on each side of the partition I3 rising and falling with pressure diierential variations. If it is desired to operate one chamber at considerably higher pressure than the other, the unit is easily redesigned to provide for a compensating hydraulic head. Differences of contact time are also readily provided. The rollers I5 and IB may be shifted up or down to give relatively longer runs in either chamber or one chamber may be operated at a greater pressure than the other to provide a difference in liquid level which eiectively changes the relative lengths of the catalyst runs in the two chambers. The modification of Figure 3 is well suited to such use.

The diagrammatic showing in Figure 2 is illustrative of use of the apparatus for cracking of hydrocarbon oils. A catalyst belt formed of dried silica-alumina. lhydrogel fibers prepared as described above is iitted about the rollers I5, Ii, Il and I8 passing through a lead bath maintained at 850 to 900 F. A gas oil charge is vaporized and the vapors superheated to about 800 F. in heater 26 and the superheated vapors are conducted to inlet 20 by line 2l. Preferably the inlet 20 is in the form of a perforated manifold to.distribute the vapors uniformly across chamber Il to pass through the catalyst belt I 0 at a rate of about one volume of liquid oil per volume of catalyst per hour. The vapors of cracked hydrocarbons issuing from catalyst I0 are withdrawn by outlets 22 and 23, which are also preferably in the form of perforated manifolds, and passed by line 28 to fractionator 29 where the cracked products are separated into suitable fractions. I

The catahrst belt, after traversing chamber Il passes to chamber I2 through the lead bath I9. 'Ihe molten lead enters the spaces among the fibers of the catalyst and thus purges it of gaseous and liquid hydrocarbons occluded in the fabric without entering the pores of the catalyst bers. From leaving the bath and entering chambers I2, the catalyst contacts an oxidizing.

gas supplied from preheater 30 through line 3| to inlet 2l. The oxidizing gas, usually air, after passing through the catalyst bed is withdrawn at outlets 24 and 25 and passed by line 22 to a stack, preferably passing through heat economizers en route. Preferably, the inlets and outlets in chamber I2 are also in the nature of manifolds to induce adequate contact across the chamber. Following regeneration, the catalyst belt is again purged by passing through the lead bath and returned to cracking chamber il.

It will be apparent that other purging means may be employed without departing from the spirit of the invention. For example, the catalyst belt may be passed through a plurality of zones with steam blanketing and purge zones interposed between cracking and regeneration zones.

I claim:

1. The process of convertingk hydrocarbons which comprises passing an endless belt of adsorbent porous fibers of silica-alumina hydrogel in a continuous path including a reaction zone, a regeneration zone and at least one purge zone wherein the belt is immersed in a bath of molten lead, passing hydrocarbon vapors at conversion conditions of temperaturez and pressure in contact with said iibers in said reaction zone,

This design provides great flexibility in oper- 7s purging hydrocarbon vapors from said nbers in said purge zone, contacting oxidizing gas with said bers in said regeneration zone and returning regenerated bers to said reaction zone.

2. The process of converting hydrocarbons which comprises passing an endless belt of adsorbent porous bers of porous silica impregnated with alumina, prepared by acid leaching a heat treated boro-silicate glass and impregnating the leached glass with alumina, in a continuous path including a reaction zone, a regeneration zone and at least one purge zone wherein the belt is immersed in a bath of molten lead, passing hydrocarbon vapors at conversion conditions of a regeneration zone and at least one purge zone,

temperature and pressure in contact with said y bers in said reaction zone, purging hydrocarbon vapors from said bers in said purge zone, contacting oxiding gas with said fibers in said regeneration zone and returning regenerated bers to said reaction zone.

3. The process of converting hydrocarbons which comprises passing an endless belt of adsorbent porous bers of silica and alumina having catalytic properties for the desired conversion in a continuous path including a reaction zone, a regeneration zone and at least one purge zone wherein the belt is immersed in a bath of molten lead, passing hydrocarbon vapors at conversion conditions of temperature and pressure in contact with said bers in said reaction zone, purg-- ing hydrocarbonvapors from said bers in said purge zone, contacting oxidizing gas with said iibers in said regeneration zone and returning regenerated bers to said reaction zone.

4. The process of converting hydrocarbons which comprises passing an endless belt of adsorbent porous bers of silica-alumina hydrogel in a continuous path including a reaction zone,

passing hydrocarbon vapors at conversion conditions of temperature and pressure in contact with said bers in said reaction zone, purging hydrocarbon vapors from said bers in said purge zone, contacting oxidizing gas with said bers in said regeneration zone and returning regenerated bers to said reaction zone.

5. The process of converting hydrocarbons which comprises passing an endless belt oi adsorbent porous bers of porous silica impregnated with alumina, prepared by acid leaching a heat treated boro-silicate glass and impregnating the leached glass with alumina, in a continuous path including a reaction zone, a regeneration zone and at least one purge zgne, passing hydrocarbon vapors at conversion conditions of temperature and pressure in contact with said bers in said reaction zone, purging hydrocarbon vapors from said bers in said purge zone, contacting oxidizing gas with said bers'in said regeneration zone and returning regenerated bers to said reaction zone.

6.- The process of converting hydrocarbons which comprises passing an endless belt of adsorbent porous fibers of silica and alumina having catalytic properties for the desired conversion in a continuous path including a reaction zone, a regeneration zone and at least one purge zone, passing hydrocarbon vapors at conversion conditions of temperature and pressure in contact with said bers in said reaction zone, purging hydrocarbon vapors from said bers in said purge zone, contacting oxidizing gas with said bers in said regeneration zone and returning regenerated bers to said reaction zone.

MILTON M. MARIBIC. 

